Manufacture of sulphonated oils and fats



Patented Jan. 16, 1934 MANUFACTURE OF AND Richard Huttenlocher,

Rhine, Germany, assi Gerbstofiwerke Carl the-Main, Germany N Drawin Serial No 23,1926

8 Claims.

any, patent application 3rd, 1926.

I have'filed in Germ F. 62727 of December 2 My invention relates to the manufacture of sulphonated oils and fats which are character- 5 ized by their stability or resistance against the action of acids, caustic lyes and solutions of alkali-earth metals compounds.

It is a well-known fact that sulphonated oils are the more stable or capable of resisting the action of acids, caustic lyes and alkali-earth metal solutions, the more organically combined sulphuric acid is contained therein, and further that a high degree of stability renders sulphonated oils particularly valuable for use in certain branches of the textile industry.

The object of my invention is to produce sulphonated oils or fats ofthe stated character and with this object in view, I have discovered, after much study and research, that by causing glacial acetic acids and $03 or equivalent substances, to react upon fatty acids and the esters thereof, sulphonates of high value respecting the requirements of the said textile industry, will be ob tained. Glacial acetic acid and S03 apparently combine to form acetyl sulphonic acid, but it is to be supposed that, as an intermediate product, acetyl-sulphuric acid will be formed which is not stable except at low temperatures and therefore, at higher temperatures, will be converted into 0 sulpho-acetic acid according to the following formula or equation:

CH3COOH+SO3=CH3COOSO2OH= HOaSCHzCOOH.

By causing one mol of castor oil, olive oil, linseed oil, train-oil, resin-oil and the like or a cor responding quantity of the fatty acids of such oils, to react with one or several mols of glacial acetic acid and S03, a complete sulphonation 40 will be ensured within a very short time while the reaction takes a smooth and even course in case that the fatty acids or the esters thereof comprise a double bond or hydroxyl group in the carbon chain.

Sulphonates produced in this manner possess a considerably larger proportion of organically bound sulphuric acid than the usual Turkey-red oils, and are capable of dissolving in diluted sulphuric acid (containing about ten percent real acid) and in caustic lyes of even up to 30 B. so

as to form perfectly clear solutions, while, on the other hand, they can combine with alkaline earth metals to form readily soluble salts.

It is obvious that sulphonated oils prepared in accordance with the present invention so as to SULPHONATED QIJLS FATS g. Application December 17, 1927 240,935, and in Germany Decembe Oberlahnstein-on-thegnor to firm Farb- &

Flesch Jr., Frankfort-on- Example 1 .I slowly add $03 to glacial acetic acid, while re constantly stirring the mixture and cooling the same, by means of any appropriate cooling agents, down to a temperature of 20 C. The proportion of the two constituents of the mixture is one mol of acetic acid to one mol of S03. I then add to the acid solution slowly one mol of olive oil, with agitation, and I continue to stir the oily mixture by means of any suitable stirring implement, for some time or until the reaction is finished which may take eight to nine hours or so.

The oil treated in this manner is perfectly and clearly soluble in water and of a very high degree of stability as hereinbefore intimated. As usual in the art it is to be washed out with a concentrated solution of sodium sulphate or sodium chloride and neutralized in the'usual manner.

Example 2 In the same manner as described in Example 1 two mols of S03 and two,mols of glacial acetic acid are mixed and caused to react whereupon one mol of ricinoleic acid is slowly added to the mixture. The subsequent washing and neutralizing operation are carried out in theusual manner.

Example 3 One mol of S03 and one mol of glacial acetic acid are caused to react in a suitable vessel and the product resulting from the reaction is carefully and slowly added to one mol of oleic acid to form a mixture which is to be cooled during the operation down to 20 C. After all of the reaction product has been added to the oleic acid, the reaction of the constituents of the mixture will be finished and the sulphona'te produced is then to be washed out and neutralized in the usual manner. p

I have further found that valuable sulphonates 110 of .the characteristics hereinbefore stated, can

, also be produced by causing glacial acetic acid Example 4 One mol of glacial acetic acid is slowly added to one mol of oleic acid, with careful agitation and adequate cooling. While the temperature is to be kept between 0 and C. one mol of hloro-sulphonic acid is slowly added to the mixture and when this operation is finished, agitation still is to be continued until the reaction approaches its end. Subsequently the sulphonate thus prepared is washed out with a suitable salt solution and neutralized in the usual way.

Example 5 Two mols of castor oil are mixed'with two mols of glacial acetic acid and the mixture is treated with two mols of chloro-sulphonic acid in the manner stated in Example 4, for sulphonating the oil. When the reaction is'over the sulphonate produced in this way is to be washed, and neutralized in a known manner.

Furthermore I have found that suitable fats and oils or the fatty acids thereof can be sulphonated by' means of S0: or chloro-sulphonic acid in the presence of glacial acetic acid, as hereinbefore described, or alternatively in the presence of other similar fatty acids andthat the latter can be readily substituted for glacial acetic acid provided that they are practicallyanhydrous or devoid of water when applied. a This modification of my invention includes the use of propionic acid, butyric acid, lactic, acid and so on which when employed for such sulphonating, will likewise lead to the production of sulphonates I of the valuable character hereinbefore indicated.

\ Again the anhydrids of the lower fatty acids such as acetic acid anhydrid, propionic acid anhydrid, butyric acid anhydrid and the chlorides of the above mentioned acids such as acetyl chloride and so on, may be employed for the purpose in view and the final products of the method, that is the sulphonate resulting therefrom, is likewise of high value in. the trade in as much as it is of a pronounced stability and comparatively rich in organically bound sulphuric acid.

the last mentioned modification in which various fatty acids of the lower order or the anhydrids or chlorides thereof are employed.

Example 6 One mol of acetyl chloride is mixed with one mol of S0: while being constantly stirred and kept cool considerably below the freezing point and the mixture thus prepared is slowly added with care to one mol of castor oil. The ultimate reaction product formed is to be washed and new tralized in the usual way.

Example 7 In a suitable autoclave one mol of aceylchloride is mixed with one mol of SOaHCl while the temperature is kept down by means of a suitable cooling agent. The liquid mixture is added to one mol of train-oil and allowed'to react thereon while the mass is constantly agitated and intensely cooled in any suitable" manner. At the same time a current of any appropriate inert gas such as nitrogen, carbonic acid or hydrogen, is to be forced through the liquid mass for the purpose of removing any hydrochloric gas evolved in the mass, and this must be continued until HCl gas ceases to escape. As usual, the product formed is subjected to a washingand neutralizing operation.

Example 8 One mol of butyric acid anhydrid is mixed with one mol of chloro-sulphonic acid and while the mixture is carefully agitated and cooled, dry air is forced through the same, by means of a suitable blower or the like, until a test shows that 1101 gas is no longer evolved in the liquid mass. The latter is then added slowly to one mol of ricinoleic acid, with agitation and while the mass. is intensely cooled in any appropriate way. 'At the end of the reaction the liquid product is to be washed out and neutralized in the usual manner.

described in detail certain ways While I have and modifications of carrying out my invention, it will be obvious to those skilled in the art that many improvements and further modifications may be made therein according to requirements desired or most suitable under diiferent circumstances; andI have set forth ,details only to enable those skilled in the art to understand how my invention may be used in certain of its preferred modifications.

What I claim is:

1. The process of sulphonating fats and oils which contain unsaturated or hydroxyl groups in the carbon chain, or the fatty acids correspondingthereto, w ch' comprises reacting upon a material of the character aforesaid with a material selected from the herein described group consisting of sulphur as such and chlorosulphonic acid in the presence of amaterial selected from the herein described group consisting of lower fatty acids, their anhydrides and chlorides.

'2. The process of sulphonating fats and oils which contain unsaturated or hydroxyl groups in the carbon chain, or the fatty acids corresponding thereto, whichcomprises reacting at a low temperature upon a material of the character aforesaid with a material selected from 'the herein described group consisting of sulphur trioxide as such and chlorosulphonic acid in the presence of a material selected from the hereindescribed group consisting of lower fatty acids,

their anhydrides and chorides. The following examples will serve to illustrate 3. The process of sulphonating fats and oils which contain unsaturated or hydroxyl groups in the carbon chain, or the fatty acids corresponding thereto, which comprises reacting upon a material of the character aforesaid with the reaction product of a material selected from the herein described group consisting of sulphur trioxide as such and chlorosulphonic acid and a material selected from the herein describe oup consisting of lower fatty acids, their anhydrides and chlorides.

4. The process of sulphonating fatty oils which contain unsaturated or hydroxyl groups in the carbon chain,.or the fatty acids corresponding thereto, which comprises reacting upon a material of the character aforesaid with the organic reaction product capable of being produced by the interaction at a low temperature of a material selected from the herein described group 150 a material of the character aforesaid with the 7 and chlorides substantially ter.

8. The process of sulphonating bodies 01' the type of castor oil, olive'oil, linseed oil, train oil, resin oil and the fatty acids corresponding thereto which comprises reacting at a low temperature and substantially in the absence of water upon a material selected from the group consisting of sulphur trioxide and chlorosulphonic acid with a material selected sisting of the lower fatty acids, their imhydrides and chlorides, whereby a sulphur containing organic reaction product capable of sulphonating such bodies is obtained, and reacting upon such a body to be sulphonated with the said reaction product.

from the group con- 

